WO2002024624A1

WO2002024624A1 - Ring opening agents of fat chemical epoxides obtained by fat chemistry and the use thereof in cosmetic preparations

Info

Publication number: WO2002024624A1
Application number: PCT/EP2001/010482
Authority: WO
Inventors: Thomas Otto Gassenmeier; Lars Zander
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2000-09-20
Filing date: 2001-09-11
Publication date: 2002-03-28
Also published as: DE10046432A1; AU2001293806A1

Abstract

The invention relates to reaction products of long-chained epoxy compounds having 10-70 C atoms with terpene alcohols of formula R1OH, with ring opening of the epoxy groups to form arrangements of formula R1O-C-C-OH wherein R1 represents the radical of a mono-, sesqui- or diterpene alcohol. Said reaction products are suitable as oil components for producing cosmetic or pharmaceutical preparations for skin care and treatment, especially emulsions, creams, salves, aerosol preparations, stick preparations or deodorants. Reaction products of epoxidised triglyceride oils with monoterpene alcohols such as geraniol, menthol, citronellol, nerol, linalool or terpineol are particularly suitable. The hydrophily and the dissolution properties of the novel terpene ethers obtained by fat chemistry can also be freely modified by adding ethylene oxide or propylene oxide. It was thereby determined that addition products on the ring opening agents of long-chained epoxy compounds obtained by fat chemistry have very interesting hair cosmetic properties, and can be added to, for example, preparations for washing or rinsing hair, causing a noticeable improvement in the sensory parameters of hair which is washed or treated by said products.

Description

"Ring opening products of oleochemical epoxides and their use in cosmetic preparations"

The invention relates to ring opening products of long-chain epoxy compounds with 10-70 carbon atoms with terpene alcohols, which are suitable as components in cosmetic preparations for cleaning and care of the hair, skin and teeth.

For the cleaning and care of the body, predominantly aqueous preparations of surface-active substances are used. These often have the disadvantage that they swell the skin too much, degrease the skin and hair too much and thus impair the condition of the skin and hair. This problem is generally countered by adding moisturizing, skin-moistening or hair-activating components to the surfactant preparations, which counteract the degreasing of the skin and give the hair better combability and more shine. Suitable additives are e.g. Oil components, e.g. Silicone oils and water-soluble polymers, especially cationic polymers with quaternary ammonium groups. Unfortunately, with regular use of preparations containing such components, the hair can be stressed by the accumulation of these substances on the hair surface.

There is therefore a need for new cosmetic oil components and hair care additives which are suitable for use in preparations for cleaning and care of the hair, skin and teeth.

Cosmetic-pharmaceutical oil components are known from EP 0 135 018 B1, which can be obtained by reacting epoxidized triglyceride oils with monohydric C 1 -C ₄ alcohols. From the ^' German Offenlegungsschrift DE 34 32 219 AI ethylene oxide addition products to reaction products of epoxidized triglyceride oils with mono- or polyvalent C ₆ -C ₆ alcohols were known as solubilizers for perfume oils. It has now been observed that reaction products of long-chain epoxy compounds with terpene alcohols are particularly interesting oleochemical oil components with new cosmetic properties.

The invention relates to reaction products of long-chain epoxy compounds with 10-70 carbon atoms with terpene alcohols of the formula R ^J OH with ring opening of the epoxy groups to form groups of the formula R'OCC-OH, in which R ^{1 is} the residue of a mono-, sesqui- or diterpene alcohol ,

The new oleochemical terpene ethers are interesting oil components for cosmetic and pharmaceutical preparations, which have good skin and mucous membrane compatibility, good stability against rancidity and a high dissolving power for cosmetic and dermatological active ingredients. They are also distinguished by the fact that they undergo a gradual hydrolysis with the elimination of the terpene alcohols in acidic media. In terms of application technology, this can be used to release monoterpene alcohols with interesting fragrance properties in a controlled manner over long periods of time and thereby give the products a pleasant fragrance over a longer period of time than would be possible with a content of conventional volatile fragrances.

The new oleochemical terpene ethers can also be modified in their hydrophilicity and solution properties by adding ethylene oxide or propylene oxide. It has been shown that addition products to the ring opening products of long-chain, oleochemical epoxy compounds have very interesting hair cosmetic properties. You can e.g. Preparations for washing or rinsing the hair are added and bring about a marked improvement in the sensory parameters of the hair washed or treated with it.

The invention therefore furthermore relates to adducts of 1-100 mol of ethylene oxide, propylene oxide or mixtures thereof with reaction products of long-chain epoxy compounds having 10-70 C atoms with mono-, sesqui- or diterpene alcohols. Linear and slightly branched epoxides of alpha-olefins or olefins with an internal double bond are suitable as long-chain epoxy compounds with 10-30 C atoms. Linear olefin epoxides with 10-30 C atoms are particularly suitable. However, the long-chain epoxy compounds are particularly preferably selected from the epoxidized unsaturated C ₁₆ -C ₂₂ fatty acid esters of mono- or polyhydric alcohols with 1-10 C atoms.

Suitable epoxy compounds are e.g. epoxidized oleic acid methyl ester, epoxidized oleic acid decyl ester, epoxidized olerlerucate, epoxidized ethylene glycol dioleate, epoxidized triolein or an epoxidized unsaturated vegetable oil such as e.g. epoxidized sperm oil or epoxidized jojoba oil. In a particularly preferred embodiment, the long-chain epoxy compound is selected from epoxidized triglyceride oils. Epoxidized triglycerides are known as so-called epoxy plasticizers and are commercially available products. They are caused by epoxidation of unsaturated oils such as Soybean oil, linseed oil, tall oil, cottonseed oil, peanut oil, palm oil, sunflower oil, rapeseed oil or claw oil are obtained with the peracetic acid process described in the American Chemical Society 67, March 1945, pages 412 to 414. Depending on the conversion ratio, all or part of the double bonds are converted into oxirane rings by the epoxidation. Triglyceride oils with an iodine number of 50-150 are particularly suitable, which, with extensive epoxidation, are converted into epoxidates with an epoxy oxygen content of 3-10% by weight.

Epoxidates with a content of 4-8% by weight epoxy oxygen are particularly suitable for the further reaction with terpene alcohols.

Both monoterpene alcohols and also sesquiterpene alcohols and diterpene alcohols can be used as terpene alcohols. Suitable monoterpene alcohols are e.g. Geraniol, Menthol, Citronellol, Nerol, Linalool, Terpineol, Borneol, Thujol, Sabinol, Myrtenol, Thymol, Verbenol, Fenchol and Piperitol.

Suitable sesquiterpene alcohols are, for example, farnesol, caryophyllenols, bisabolol, patchulial alcohol and betulenol. Suitable diterpene alcohols are, for example, phytol, retinol and geranylgeraniol. The terpene alcohols for the reaction products according to the invention are particularly preferably selected from the group of the monoterpene alcohols geraniol, menthol, citronellol, nerol, linalool and terpineol.

The reaction of the long chain epoxy compounds with the terpene alcohols is preferred in the presence of an acid catalyst, e.g. performed by concentrated sulfuric acid. A particularly preferred ring opening process is described in DE 44 46 877 AI, using fluoroalkanesulfonic acids as acid catalysts.

The reaction leads to the opening of the epoxy groups (oxirane rings) with the formation of a group R ^ -CC-OH, in which R ^{1 is} the rest of the mono-, sesqui- or diterpene alcohol. For the reaction, the terpene alcohol is used in excess with respect to the epoxy groups in order to achieve a large opening of all oxirane groups. The excess terpene alcohol can be removed by distillation after the reaction. However, one can also carry out a molar reaction, for example with sesqui or diterpene alcohols, and finally add an excess of a low-boiling alcohol, for example of methanol or ethanol, to open residual epoxy groups, which can be distilled off after all epoxy groups have been opened.

In this way, liquid, oxidation-stable, skin and mucous membrane compatible oil components are obtained with monoterpene alcohols. These have good dissolving power for cosmetic and dermatological active ingredients and good dispersing power for pigments. They are therefore particularly suitable as oil components for the production of cosmetic and therapeutic preparations for the care and treatment of the skin, in particular emulsions, creams, ointments, aerosol preparations, stick preparations and deodorants.

The use in deodorants is particularly interesting because the gradual release of the pleasantly smelling terpene alcohols on the skin enables a particularly long-lasting deodorant effect. The addition of ethylene oxide, propylene oxide or mixtures thereof onto the reaction products according to the invention of long-chain epoxy compounds having 10-70 carbon atoms with terpene alcohols is carried out according to the known process of ethoxylation or propoxylation in the presence of acidic or basic catalysts. The addition products obtained thereby are mixtures of homologous polyglycol ethers whose average degree of ethoxylation or propoxylation corresponds to the molar amount of the alkylene oxide added. With increasing degree of ethoxylation, the hydrophilicity of these addition products also increases, which gradually become water-soluble when 50-70% by weight of ethylene oxide is added (based on the addition product).

The adducts of ethylene oxide and / or propylene oxide with the oleochemical terpene ethers according to the invention have surface-active properties and can also be used as emulsifiers, co-emulsifiers and solubilization aids. In addition, they show interesting hair cosmetic properties and are particularly suitable as conditioning components in preparations for washing and rinsing the hair, in particular an improvement in the hair shine, the manageability, the volume, the softness and the feel of the hair.

Another object of the invention is therefore the use of the addition products of 1-100 mol ethylene oxide and / or propylene oxide to the reaction products according to the invention of long-chain epoxy compounds with 10-70 carbon atoms with terpene alcohols as hair-activating component in preparations for cleaning and care of the hair. Such preparations can e.g. Shampoos and hair rinses, hair dyes, permanent wave fixatives or other rinse-off products.

A particularly preferred embodiment of the invention are preparations for cleaning the hair and skin containing surface-active substances, the addition products of 1-100 mol ethylene oxide and / or propylene oxide onto reaction products according to the invention of long-chain epoxy compounds with terpene alcohols in an amount of 0.1-10 % By weight. The adducts of ethylene oxide and propylene oxide with the oleochemical terpene ether according to the invention have a particularly good compatibility with cosmetic surfactant systems, as are customary in skin and hair cleansers. They have no foam-suppressing properties and, in mixtures with anionic surfactants, for example with alkyl (C ₁ -C ₁₆ ) polyglycol ether sulfates, show a rather thickening and foam-stabilizing effect. The same beneficial effects are also observed in surfactant combinations of anionic, zwitterionic and nonionic surfactants. The following examples are intended to explain the subject matter of the invention in more detail:

Examples

1. Synthesis examples

1.1) Production of the ring opening product from epoxidized soybean oil and geraniol

Starting materials 436 g Edenol D81 (4) 225 g geraniol E250 (6) 0.074 g H ₂ SO ₄ 0.41 g Lupranol 3402 (5)

Execution:

The geraniol and the trifluoromethanesulfonic acid were presented. The Edenol D81 was added dropwise at 90 ° C. in the course of 20 minutes, an exotherm being evident. After three hours with stirring at 95 ° C, the epoxy content had dropped to below 0.05%. The reaction was stopped and the reaction mixture was neutralized with Lupranol 3402.

Excess geraniol was then distilled off under high vacuum and the product was thus obtained as a clear, yellow, viscous oil.

Characteristics of the product: clear, yellow, viscous oil odorless; Odor development at an acidic pH (elimination of geraniol)

> OH number: 130 (theoretical OH number: 140.5)> acid number: 0.6

1.2) Preparation of the adduct of about 10 moles of ethylene oxide per hydroxyl equivalent of the ring opening product according to Example 1

starting materials

150 g of the ring opening product according to Example 1 150 g of ethylene oxide 1.5 g of KOH (aqueous solution) 1.2 g of lactic acid

execution

The ring opening product was reacted with the ethylene oxide in an autoclave at 5 bar and 140 ° C. for 3 hours. The reaction mixture was then neutralized with lactic acid. A clear, light brown oil was thus obtained as the product.

Characteristics of the product:

> clear, light brown oil OH number: 99

> Acid number: 2.2

2. Application test

The following shampoo formulations were produced:

The data relate to% by weight of anhydrous active substance.

Compositions 2.1 to 2.3 were used for the treatment of 2 g, pre-cleaned locks of hair. For this purpose, 1 g of the composition per strand was left to act at 20 ° C. for one minute, then the hair was rinsed out and dried under air-conditioned conditions.

The sensory evaluation of the parameters hair gloss, manageability, volume, softness and feel of the hair showed clear advantages for the formulation 2.1 compared to the comparative products according to formulation 2.2 and 2.3. The following commercial products were used:

l. Texapon ^® N25 Sodium Laureth Sulfate, 28% in water 2. Dehyton ^® K Cocamidopropyl Betaine, 30% in water 3. Plantacare ^® 2000 UP C ₈ -Cι ₆ fatty alcohol (1.4) glucoside, 50% in water

4. Edenol ^® D81 epoxidized soybean oil, epoxy oxygen 6.7% by weight

Ol 5. Lupranol® ^® 3402 polyether tetrol (amine-based) 6. geraniol E250 3, 7-dimethyl-2,6-octadiene 1

The following adduct was used for comparison:

7. VI: adduct of 50% by weight of ethylene oxide with a ring opening product of soybean oil epoxide and methanol

Claims

Claims:

1. Reaction products of long-chain epoxy compounds with 10-70 carbon atoms with terpene alcohols of the formula R ^ H with ring opening of the epoxy groups to form groups of the formula R ^ -CC-OH, in which R ^{1 is} the residue of a mono-, sesqui- or diterpene alcohol.

2. Reaction products according to claim 1, characterized in that the long-chain epoxy compounds are selected from the epoxidized, unsaturated C ₁₆ -C ₂ fatty acid esters of mono- or polyhydric alcohols with 1-10 C-

Atoms.

3. Reaction products according to one of claims 1 or 2, characterized in that the long-chain epoxy compounds are selected from epoxidized triglyceride oils.

4. Reaction products according to one of claims 1 to 3, characterized in that the terpene alcohols are selected from the group of the monoterpene alcohols geraniol, menthol, citronellol, nerol, linalool and terpineol.

5. Addition products of 1 to 100 moles of ethylene oxide and / or propylene oxide onto reaction products according to one of claims 1 to 4.

6. Use of the reaction products according to one of claims 1 to 4 as an oil component for the production of cosmetic or therapeutic

Preparations for the care and treatment of the skin, in particular emulsions, creams, ointments, aerosol preparations, stick preparations and deodorants.

7. preparations for cleaning the hair or skin containing surface-active substances, characterized in that the addition products of 1-100 mol ethylene oxide and / or propylene oxide according to claim 5 in an amount of 0.1 to 10 wt .-% therein are included.